One‐Pot Synthesis of 2,5‐Furandicarboxylic Acid from 2‐Furoic Acid by a Pd‐catalyzed Bromination–Hydroxycarbonylation Tandem Reaction in Acetate Buffer
Yin‐Qing Yao,
Kai‐Chun Zhao,
Yi‐Ying Zhuang,
Xiao‐Chao Chen,
Prof. Dr. Yong Lu,
Prof. Dr. Ye Liu
Affiliations
Yin‐Qing Yao
Shanghai Key Laboratory of Green Chemistry and Chemical Processes School of Chemistry and Molecular Engineering East China Normal University 200062 Shanghai China
Kai‐Chun Zhao
Shanghai Key Laboratory of Green Chemistry and Chemical Processes School of Chemistry and Molecular Engineering East China Normal University 200062 Shanghai China
Yi‐Ying Zhuang
Shanghai Key Laboratory of Green Chemistry and Chemical Processes School of Chemistry and Molecular Engineering East China Normal University 200062 Shanghai China
Xiao‐Chao Chen
Shanghai Key Laboratory of Green Chemistry and Chemical Processes School of Chemistry and Molecular Engineering East China Normal University 200062 Shanghai China
Prof. Dr. Yong Lu
Shanghai Key Laboratory of Green Chemistry and Chemical Processes School of Chemistry and Molecular Engineering East China Normal University 200062 Shanghai China
Prof. Dr. Ye Liu
Shanghai Key Laboratory of Green Chemistry and Chemical Processes School of Chemistry and Molecular Engineering East China Normal University 200062 Shanghai China
Abstract The one‐pot synthesis of 2,5‐furandicarboxylic acid from 2‐furoic acid with a yield of 57 % was achieved for the first time using a Pd‐catalyzed bromination‐hydroxycarbonylation tandem reaction in HOAc‐NaOAc buffer. This synthetic protocol shows major improvements compared to previously reported methods, such as using biomass‐based 2‐furoic acid as low‐cost raw material, one‐pot synthesis without isolation of intermediate products, and no need for an acidification procedure. Experiments indicate that the involved Xantphos‐modified Pd‐catalyst and the buffer solution play significant promoting roles for each individual reaction whereas Br2 (as the brominating reagent) had a negative effect on the second hydroxycarbonylation step, while CO was deleterious for the first bromination step. Hence, in this practical one‐pot synthesis, Br2 should be consumed in the first bromination step as fully as possible, and CO is introduced after the first bromination step has been completed.
